KR102507969B1 - adsorption device - Google Patents

Abstract

This adsorbent sheet provides improved performance in vapor adsorption applications over conventional canisters and other emission control equipment. The absorbent sheet may be manufactured as part of a small, lightweight canister, or may be integrated into the fuel tank. The absorbent sheet may be used as part of an onboard refueling vapor recovery system to control volatile organic compound emissions from fuel tanks of gasoline vehicles, such as automobiles.

Description

adsorption device

The present invention relates to an adsorption device.

CITATION OF RELATED APPLICATIONS: This application claims the benefit of priority from U.S. Provisional Application No. 62/452,704, filed January 31, 2017, the entirety of which is incorporated herein by reference.

Government Rights: N/A

Parties to Joint Research Agreement: N/A

Substitution by citation of material submitted on compact disc: not applicable

Volatile exhaust gases from gasoline and other liquid hydrocarbon fuels are a major source of air pollution because the various hydrocarbons contained in those fuels can form photochemical smog when exposed to sunlight. The smog compounds and hydrocarbons themselves not only harm human and animal health, but also cause environmental damage. Volatile exhaust gases are a particular problem when refueling a motor vehicle because "empty" fuel tanks are in fact filled with fuel vapor, and filling the fuel tank with liquid fuel draws the vapors out of the tank. Volatile exhaust gases are also generated when the fuel in the tank is heated, for example due to hot ambient conditions or hot exhaust system components. If fuel vapors are not controlled, they will be emitted as pollution in the atmosphere.

In the automotive sector, gasoline vapor is usually recovered by an Onboard Refueling Vapor Recovery system (ORVR) during refueling. These devices include a number of components designed to capture the vapors released from fueling gasoline so that the engine can later combust them. Vapor is sealed in the fuel tank by a specially designed tank and fuel filler neck, and excess vapor is captured and adsorbed in a chemical canister. While the engine is running, the engine control unit (ECU) releases the adsorbed vapors from the canister and allows them to enter the engine fuel system, allowing the gasoline vapors to burn as usual and the canister to be used again.

Although ORVR systems have been successful in reducing vapor emissions, they still have problems. Chemical canisters are filled with loose adsorbent particulates such as activated carbon or charcoal which are cumbersome to handle and package. These canisters are bulky and heavy because the adsorbent particulates cannot physically support themselves, and stringent emissions regulations now prohibit the release of even small amounts of vapor, requiring higher adsorbent capacities. Manufacture, maintenance and disposal of the canisters are also cumbersome and complex due to the loose adsorbent particulates, and the complexity of the ORVR unit increases the cost of each vehicle while reducing beneficial passenger and cargo space. As automakers need to reduce the weight of all components to meet increasing fuel economy targets as well as lower costs and more passenger and cargo space, smaller, lighter, and There is a growing need for new ORVR devices that are simpler and more cost effective.

In one embodiment, the present invention discloses an adsorbent sheet having improved performance over an equivalent amount of adsorbent compound provided as a powder.

In another embodiment, the present invention discloses a sheet of absorbent material contained within a housing.

In another embodiment, the present invention discloses a sheet of absorbent material contained directly within a fuel tank instead of excluding a housing.

In another embodiment, the present invention discloses an emission control system, such as an ORVR, that includes an absorbent sheet. The absorbent sheet within the ORVR may be contained within the housing, or the housing may be excluded.

The present invention also relates to the embodiments listed below:

1. As a sorbent material sheet product,

at least two adsorbent sheets, each adsorbent sheet having a defined top surface and a bottom surface as a total total surface area, each adsorbent sheet including an adsorbent and a binder, and wherein adjacent top and bottom surfaces of the individual sheets are substantially wherein each absorbent sheet is stacked and arranged so that they are parallel to each other and aligned to allow fluid to flow between at least the adjacent top and bottom surfaces.

2. The absorbent sheet product of embodiment 1, wherein the absorbent sheet product has a BWC stacking multiplier ratio from about 1.1 to about 1.3, wherein the BWC stacking multiplier ratio is defined by the formula:

BWC Stacking Drainage Ratio = [ (Measured BWC of the entire adsorbent sheet product) / (BWC of each adsorbent sheet measured externally apart from the above product) ] / number of adsorbent sheets in the adsorbent sheet product.

3. The adsorbent sheet of embodiment 1, wherein the individual adsorbent sheet has a BWC value, measured individually, that is 5-15% greater than the BWC of an equal weight of adsorbent in pelletized or powdered form. product.

4. The method of embodiment 1, wherein the at least one absorbent sheet is laminated in a planar shape, a spiral-cylindrical wound shape, an elliptical wound shape, an elongated rectangular bar wound shape, a folded shape, or an “S” shape. The absorbent sheet product of claim 1 , wherein the absorbent sheet product is configured in a rounded shape, a shape formed into concentric cylinders, a shape formed into concentric ovals, a shape formed into concentric rectangular rods, or a combination of the above shapes.

5. The absorbent sheet product of embodiment 1, wherein the at least one absorbent sheet has protrusions and/or depressions.

6. The absorbent sheet product of embodiment 5, wherein the projections and/or depressions are present and nested on adjacent sheets.

7. The absorbent sheet product of embodiment 5, wherein the protrusions and/or depressions are on adjacent sheets and are not overlapping.

8. The absorbent sheet product of embodiment 1, wherein the absorbent sheet product has a void volume of about 10% or less.

9. The absorbent sheet product of embodiment 1, wherein each individual absorbent sheet has a density from about 0.08 g/cc to about 1.5 g/cc.

10. The absorbent sheet product of embodiment 1, wherein the absorbent sheet product has a BWC greater than about 10 g/100 cc.

11. The absorbent sheet product of embodiment 1, wherein the absorbent sheet product has a BWC of about 7.0 g/100 cc to about 30 g/100 cc.

12. The method of embodiment 1, wherein the adsorbent sheet comprises adsorbent particles having at least two groups of different average particle diameters, wherein the ratio of the average particle diameters of the two groups is from about 1:2 to about 1: 10, an adsorbent sheet product.

13. The absorbent material of embodiment 1, wherein the amount of binder and the amount of absorbent sheet product are in a gradient such that the amount of binder is highest on the outside of the absorbent sheet product and lowest on the inside of the absorbent sheet product. sheet products.

14. The absorbent sheet product of embodiment 1, wherein the at least one absorbent sheet comprises holes, cutouts or openings.

15. The method of embodiment 1, wherein the binder is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO) , UV curable acrylate, UV curable methacrylate, thermoset divinyl ether, polybutylene terephthalate, acetal or polyoxymethylene resin, fluoroelastomer, perfluoroelastomer (FFKM) and/or tetrafluoroethylene/propylene Rubber (FEPM), aramid polymer, para-aramid polymer, meta-aramid polymer, poly trimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented An absorbent sheet product comprising polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof.

16. As a rolled absorbent sheet product,

An adsorbent sheet having a defined upper surface and a lower surface as a total surface area, comprising an adsorbent and a binder,

wherein the absorbent sheet is helically wound to form adjacent sheet layers that permit fluid to flow around and between the adjacent sheet layers.

17. The rolled absorbent sheet product of embodiment 16, wherein the rolled absorbent sheet has a BWC of at least 10% greater than the BWC of the same non-rolled absorbent sheet.

18. The rolled absorbent sheet product of embodiment 16, wherein the rolled absorbent sheet product has a BWC of at least 10% greater than the BWC of a substantially equivalent amount of pelletized or powdered form of the absorbent material within the absorbent sheet.

19. The rolled absorbent material sheet product of embodiment 16, wherein the rolled absorbent sheet product has a generally cylindrical shape with a length greater than a diameter.

20. The rolled absorbent sheet product according to embodiment 16, wherein the rolled absorbent sheet product is wound at an average roll density of 500-700 kg/m 3 .

21. The rolled absorbent sheet product of embodiment 16, wherein the rolled absorbent sheet product has a butane working capacity greater than about 10 g/100 cc.

22. The rolled absorbent sheet product of embodiment 16, wherein the rolled absorbent sheet product has a butane adsorbent and desorption capacity of about 7.0 g/100 cc to about 30 g/100 cc.

23. The rolled absorbent sheet product of embodiment 16, wherein the rolled absorbent sheet comprises at least two groups of absorbent particles, each group of the at least two groups having a different average particle diameter.

24. The method of embodiment 16, wherein the rolled adsorbent sheet comprises adsorbent particles having at least two groups of different average particle diameters, and the ratio of the average particle diameters of the two groups is from about 1:2 to about 1 : 10, a roll type adsorbent sheet product.

25. The method of embodiment 16, wherein the binder is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO) , UV curable acrylate, UV curable methacrylate, thermoset divinyl ether, polybutylene terephthalate, acetal or polyoxymethylene resin, fluoroelastomer, perfluoroelastomer (FFKM) and/or tetrafluoroethylene/propylene Rubber (FEPM), aramid polymer, para-aramid polymer, meta-aramid polymer, poly trimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented A rolled absorbent sheet product comprising polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof.

26. A canister for vapor adsorption comprising:

The absorbent sheet product of the first embodiment, and

A housing at least partially enclosing the absorbent sheet product of the first embodiment.

27. The canister of embodiment 26, wherein the housing is flexible.

28. The method of embodiment 26, wherein the housing is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO) , UV curable acrylate, UV curable methacrylate, thermoset divinyl ether, polybutylene terephthalate, acetal or polyoxymethylene resin, fluoroelastomer perfluoroelastomer (FFKM) and/or tetrafluoroethylene/propylene rubber (FEPM), aramid polymer, para-aramid, meta-aramid polymer, polytrimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof.

29. The canister of embodiment 26, wherein the shape of the housing substantially matches the shape of the absorbent sheet product of the first embodiment contained therein.

30. The canister of embodiment 26 further comprising at least one structure selected from tubes, inlets, outlets, sensors, valves and fluid channels.

31. A canister for vapor adsorption comprising:

a. The rolled absorbent sheet product of the sixteenth embodiment, and

b. A housing at least partially enclosing the rolled absorbent sheet product of the sixteenth embodiment.

32. The canister of embodiment 31, wherein the housing is flexible.

33. The method of embodiment 31, wherein the housing is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO) , UV curable acrylate, UV curable methacrylate, thermoset divinyl ether, polybutylene terephthalate, acetal or polyoxymethylene resin, fluoroelastomer perfluoroelastomer (FFKM) and/or tetrafluoroethylene/propylene rubber (FEPM), aramid polymer, para-aramid, meta-aramid polymer, polytrimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof.

34. The canister of embodiment 31, wherein the shape of the housing substantially matches the shape of the rolled absorbent sheet product of embodiment 16 contained therein.

35. The canister of embodiment 31 further comprising at least one structure selected from tubes, inlets, outlets, sensors, valves and fluid channels.

36. A tank with essential vapor adsorption function,

tank structure;

at least one adsorbent sheet having a defined upper and lower surface of each sheet as total total surface area, each adsorbent sheet comprising an adsorbent and a binder; and

and at least one securing device for securing the adsorbent sheet to a surface of the tank that is not regularly immersed in the volatile liquid contained within the tank.

37. The tank of embodiment 36, wherein the fixing device is an adhesive layer formed between one side of the adsorbent sheet and a wall of the tank.

38. The method of embodiment 36, wherein the adhesive is a pressure sensitive adhesive, UV curable adhesive, thermosetting adhesive, hot melt adhesive, reactive multi-part adhesive, acrylic and (meth)acrylic adhesive, acrylic and at least one of latex and (meth)acrylate adhesives, epoxy adhesives in one- or two-part formulations, urethane adhesives, and copolymers and combinations thereof.

39. The method of embodiment 36, wherein the tank comprises a fuel pump, a fuel supply line, a fuel return line, an atmospheric exhaust line, a port, a valve, a sensor, an air intake, an open cell foam, a baffle, A tank further comprising at least one of a bladder and a combination of the foregoing.

40. The tank of embodiment 36, wherein the tank is a fuel tank in a “ship in a bottle” configuration.

41. An onboard fueling vapor recovery device comprising the absorbent sheet product of the first embodiment.

42. An onboard fueling vapor recovery device comprising the rolled adsorbent sheet product of embodiment 16.

43. An onboard fueling vapor recovery device comprising the vapor adsorption canister of embodiment 26.

44. An onboard fueling vapor recovery device comprising the vapor adsorption canister of embodiment 31.

45. An onboard fueling vapor recovery device comprising a tank having the essential vapor adsorption function of embodiment 36.

Prior to describing the compositions and methods of the present invention, it should be understood that the present invention is not limited to the particular method, composition or methodology described herein as it may vary. Also, the terms used in the detailed description are only for the purpose of describing specific forms or embodiments, and are not intended to limit the scope of the present invention, which is to be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods, devices and materials are described herein. All publications mentioned herein are incorporated herein by reference in their entirety. Nothing herein is to be construed as an admission that the present invention does not predate such disclosure by prior invention.

As used in this specification and the appended claims, the singular forms "a", "an" and "the" should be understood to include references to the plural unless the context clearly dictates otherwise. Thus, for example, reference to “a combustion chamber” is a reference to “one or more combustion chambers” and equivalents thereof known in the art, and the like.

As used herein, the term “about” means ±10% of the numerical value of the number in which the term is used. Thus, about 50% means in the range of 45% to 55%.

As used herein, the term "sorbent material" encompasses all known materials from any source capable of adsorbing liquids and/or gases. For example, adsorbent materials include, but are not limited to, activated carbon, natural and synthetic zeolites, silica, silica gel, alumina, zirconia, and diatomaceous earth.

As used herein, the term "may" means that the subsequently listed elements may or may not be included in the embodiment. For example, an embodiment that may include a polymeric matrix means that the embodiment may include the polymeric matrix, but it is also contemplated that the embodiment may exclude the polymeric matrix.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Herein, the description and claims of multiple sheets of adsorbent material are intended to mean that there are multiple individual sheets having sides and/or surfaces proximate to one another. Alternatively, the description and claims of multiple sheets of adsorbent material may be laminated, rolled, or otherwise constructed, where there is only a single sheet, but the single sheet itself is rolled or folded to have sides and/or surfaces proximate to one another. It is intended to mean that a lump of a sheet is manufactured. The term also connotes the stacking of a number of sheets together followed by winding or otherwise folding to form a single mass of alternating layers.

Embodiments of the present invention relate to devices comprising one or more adsorbent sheets, and methods of making adsorbent sheets and devices comprising these sheets. In various embodiments, the absorbent sheet may consist of an absorbent material and a binder and have a thickness of less than about 1 mm. Devices of various embodiments may include a housing and one or more sheets of absorbent material. In some embodiments, the device may have a porosity greater than about 10% of the total volume of the housing.

absorbent sheet

The adsorbent sheet of the present invention may include any of the adsorbents described above, including, but not limited to, activated carbon, natural and synthetic zeolites, silica, silica gel, alumina, zirconia, and diatomaceous earth, and in certain embodiments, the The adsorbent sheet may be made of activated carbon. These adsorbents may be used alone or in combination.

The activated carbon can be of various grades and types selected based on performance requirements, cost and other considerations. The activated carbon may be granulated by re-agglomeration of powder, granulated by crushing or sizing nut shells, wood, coal, or pellets produced by extrusion, or granulated activated carbon in powder form. The activated carbon may be formed and activated through a carbonization process. Raw materials such as wood, nutshells, coal, pitch, etc. are oxidized and devolatilized, and steam and/or carbon dioxide are vaporized to form a pore structure useful for adsorption in activated carbon. The initial oxidation and devolatilization process may include chemical treatment with dehydrating chemicals such as phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, and combinations thereof.

A variety of activation processes are known in the art. The most useful method of providing activated carbon to the absorbent sheet of the claimed invention comprises providing wood and/or wood by-products, acid treating the wood and/or wood by-products by exposing them to phosphoric acid, and steam and/or carbon dioxide gas. and carbonizing the wood and/or wood by-products using fire. This method produces activated carbon particles with the best butane adsorption and desorption capacity ("BWC"), a measure of activated carbon performance. More details of the BWC test and results are described in the Examples.

The activated carbon is sugar cane dregs, bamboo, coconut hulls, peat, wood such as hardwood and softwood feedstock in the form of sawdust and shavings, lignite, coal and coal tar, petroleum pitch, asphalt and bitumen, corn stalks and hulls, wheat straw, It may be formed from materials including ginseng, rice and rice bran, nutshells, and combinations thereof.

The adsorbent sheet may further include one or more binders. Examples include, but are not limited to specific binders, polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable acrylates, UV curable methacrylates, thermosetting divinyl ethers, polybutylene terephthalate, acetal or polyoxymethylene resins, fluoroelastomers such as perfluoroelastomers (FFKM) and tetrafluoro ethylene/propylene rubber (FEPM) ), aramid polymers such as para-aramid and meta-aramid polymers, poly trimethylene terephthalate, ethylene acrylic elastomers, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP ), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof. The binder may be thermoplastic or thermosetting depending on conditions, and may include a mixture of thermoplastic and thermosetting compounds.

The amount of binder can be from about 2% to about 30% by weight of the total composition, and in certain embodiments, the amount of binder can be from about 2% to about 20% or from about 2% to about 10% by weight of the total composition. can be, or can be any individual amount or range of amounts encompassed by the above exemplary amounts. In some embodiments, the adsorbent sheet may include solvents that may be present in minor residual amounts, generally for example less than 10%, less than 5% or less than 2% by weight and greater than about 0.1% or 0.2% by weight. . In particular, in some embodiments, the absorbent sheet may be solvent free (0%).

In some embodiments, the absorbent sheet may have a thickness of less than about 1 mm, about 0.01 mm to about 1.0 mm, about 0.02 mm to about 0.90 mm, about 0.05 to about 0.95 mm, about 0.05 to about 0.90 mm, or It may have any individual thickness or range of thicknesses included in the above exemplary ranges. The absorbent sheet of the various embodiments above can have a density of from about 0.05 g/cc to about 2.0 g/cc, as measured by the Particle Density Test, and in other embodiments, the absorbent sheet, as measured by the Particle Density Test, It can have a density of 0.08 g/cc to about 1.5 g/cc, about 0.1 g/cc to about 1.3 g/cc, or any density or density range included in the above exemplary ranges. In some embodiments, the absorbent sheet may have a resistivity of less than 20 ohm-cm, and in certain embodiments, the absorbent sheet may have a resistivity between about 10 ohm-cm and about 20 ohm-cm, between about 8 ohm-cm and about 18 ohm-cm. cm, or any individual resistivity or resistivity range included in the above exemplary ranges. The BWC for each adsorbent sheet can be greater than about 10 g/100 cc, and in some embodiments, the BWC is between about 7.0 g/100 cc and about 30 g/100 cc, between about 8.0 g/100 cc and about 25 g /100 cc, about 10 g/100 cc to about 20 g/100 cc, about 10 g/100 cc to about 15 g/100 cc, about 11 g/100 cc to about 15 g/100 cc, about 12 g/ 100 cc to about 15 g/100 cc or any individual BWC or BWC range included in the above exemplary ranges. In another example, the BWC is about 9 g / 100 cc to about 15 g / 100 cc, about 12 g / 100 cc to about 20 g / 100 cc, about 13 g / 100 cc to about 20 g / 100 cc, about 14 g/100 cc to about 20 g/100 cc or about 15 g/100 cc to about 20 g/100 cc. It is also contemplated to combine any of the endpoints of the above ranges to create new and distinct ranges.

The absorbent sheet of the present invention has better performance, as measured by BWC, than conventional absorbent materials provided in powder or other particulate form.

The absorbent material sheets of the embodiment can be made by any process. In some embodiments, the sorbent sheet is prepared by grinding granulated or pelletized sorbent material into a powder, mixing the powder with a binder to form a mixture, heating and blending the mixture, and rolling the mixture to form a sorbent material. It can be manufactured by forming a sheet. The milling step may have an average particle diameter of from about 0.001 mm to about 0.2 mm, from about 0.005 mm to about 0.1 mm, from about 0.01 mm to about 0.075 mm, or any individual particle diameter or range of particle diameters falling within these exemplary ranges. In certain embodiments, the ground sorbent particles may have an average particle diameter of from about 0.001 mm to about 0.01 mm. The mixing step of mixing the powder with the binder may comprise from about 2% to about 20% or about 2% to about 10% by weight of the total composition of the adsorbent particle powder, or any individual amount or It may include mixing in a range of amounts. Heating may be performed at any temperature sufficient to remove residual solvent, such as from about 50° C. to about 200° C., for example.

In the adsorbent sheet of the present invention, particles of different sizes may be variously distributed in order to increase the packing efficiency of the powder in the adsorbent sheet. Selection of different sized particles can also improve the rheological properties of the powder and surrounding binder, resulting in improved mixing and uniform particle distribution prior to forming the corresponding adsorbent sheet. In some embodiments, the particles of the absorbent sheet may have a single particle size distribution, and in other embodiments, the particles may have two different particle size distributions. In a further embodiment, the particles may have at least three different particle size distributions.

The average particle size of at least two different particle groups each having a specific size distribution may be selected such that the particles have a ratio of about 1:1 to about 1:15. In other embodiments, the average particle size of the two different particle populations may have a ratio of about 1:2 to about 1:10. Also, the average particle size may have a ratio of about 1:2 to about 1:5, or any combination of the ratios listed above.

The adsorbent sheet has a significantly higher adsorbent capacity than prior art fuel vapor recovery canisters for a given volume and weight. These capabilities can be used in a variety of ways. In some embodiments, the absorbent sheet may improve pollution control processes in jurisdictions where such high levels of control are required. In other embodiments, the overall size, cost and weight of the ORVR may be reduced for a particular level of performance. In a further embodiment, it is possible to design an ORVR adsorption device with improved performance over conventional adsorption canisters, allowing designers to avoid costly and complex returnless fuel pumps required to reduce evaporative emissions in other situations. system can be omitted. In addition, high performance adsorption units do not require an active condensate vapor system, avoiding the size, weight and cost of compressor pumps and condensate storage tanks. However, it should also be understood that ORVR adsorbent devices using the absorbent sheets of the present invention are exceptionally high performance compared to conventional systems and can be combined with these devices for minimal size, weight and cost penalties.

The absorbent sheets can be constructed together in a variety of ways depending on the physical space they must match, the device performance required, and the features included proximate to the sheet. In some embodiments, the sheet of absorbent material may be gathered, include folds, and/or include holes or openings to increase the surface area of that absorbent sheet exposed to fluid flowing therethrough, such that for a given total sheet surface area can increase performance. Various corrugations, folds, holes and openings can be sized and placed to fit internal and external features such as fluid channels, tubing, sensors and valves. The folded portion of the absorbent sheet may take various forms, such as a cylindrical or elliptical spiral wrapped configuration. The fold may be an "S" shape or a convex or concave "C" shape depending on the desired device dimensions and/or other internal or external features desired. In addition, the absorbent sheets may be stacked in a flat or curved shape, and the stacked sheets may have a square, rectangular, circular, oval, or other irregular shape as necessary to fit a desired space. This, in combination with the housing features discussed below, allows devices formed from the absorbent sheet to fit into smaller, irregularly shaped spaces than prior art canister devices, thereby maximizing vehicle interior space.

In addition to the foregoing configuration, the absorbent sheet may also include surface features. In some embodiments, the absorbent sheet may include protrusions, and in other embodiments, the absorbent sheet may include depressions. These surface features may be combined within the same sheet. Including protrusions and/or depressions in the sheets can be used to form various configurations between the sheets, such as stacking or wrapping the sheets. For example, the sheets may be aligned such that the protrusions and/or depressions overlap each other, thereby bringing adjacent sheets closer together. In addition, the sheets may be aligned such that the projections and/or depressions do not overlap each other, forming a gap between adjacent sheets. The alignment can be used to form a variety of open and closed channels for vapor adsorption between the sheets.

Sorbent Sheet Products

The above-mentioned adsorbent sheets are combined into an adsorbent sheet product. Combinations of the absorbent sheets utilize one or more of the aforementioned features, such as increased surface area/volume ratio, reduced void space, improved absorbent performance, and the like. Generally, individual absorbent sheets are placed next to each other to form an absorbent sheet product comprising stacked, rolled, wound, folded and/or laminated sheets such that the surfaces of the absorbent sheets are in close proximity or adjacent to each other. . Whatever the arrangement, the objective is to maximize the surface area of the sheet exposed to vapor, fluid and/or gas streams, thereby maximizing the performance of the absorbent sheet.

Stacked Sorbent Sheet Product : The laminated absorbent sheet product of the present invention comprises two or more sheets of absorbent material having a known total surface area each defining an upper surface and a lower surface, wherein each sheet of absorbent material comprises an absorbent material and a binder. do; The respective absorbent sheets are stacked and arranged such that adjacent upper and lower surfaces are substantially identical to each other and are aligned such that fluid flows between at least the adjacent upper and lower surfaces.

This arrangement leads to improved BWC. For example, each individual sheet of absorbent material may have a BWC of about 12, and the stacked absorbent sheet media may have a BWC of at least about 1-10%, at least about 5-15%, at least about 2-20% of the sum of the BWCs of the individual sheets. %, at least about 5-10% or at least about 7% higher BWC. The absorbent sheet media of claim 1, wherein the laminated absorbent sheet product has a BWC that is at least about 5% higher than the BWC of an unlaminated sheet having the same known surface area.

Further, the performance improvement of the laminated absorbent sheet product of the present invention can be measured as the performance of that product with a given amount of activated carbon relative to the performance of the same amount and grade of activated carbon when provided in pelletized or powdered form in a canister. there is. In some embodiments, the layered absorbent sheet product contains greater than about 3%, greater than about 5%, greater than about 7%, greater than about 9%, greater than about 9%, relative to the same amount and grade of activated carbon in pelletized or powdered form in a canister. have a BWC that is greater than 10%, greater than about 12%, greater than about 14% and greater than about 16%. Performances in ranges based on these amounts are also contemplated, such as greater than about 5-14%, greater than about 5-10%, greater than about 10-16%, and the like.

It should be noted that these improvements are measured only between the weights of the pelletized or powdered activated carbon and the layered absorbent sheet product, without considering other improvements in the laminated absorbent sheet product. One major difference noted above is the omission of the rigid canister body required in other cases. Omission of the rigid canister body required in prior art systems involving pelletized or powdered activated carbon due to the loose activated carbon not being able to support itself would lead to additional weight savings and thus additional performance at a given weight. can

The laminated absorbent sheet product has a BWC that is at least 10% greater than the BWC of the same weight of the absorbent in pelletized/powdered form in the absorbent sheet. The laminated adsorbent sheet product has a butane adsorption and desorption capacity of greater than about 10 g/100 cc. The layered adsorbent sheet product has from about 7.0 g/100 cc to greater than about 30 g/100 cc, or greater than about 12 g/100 cc, or greater than about 13 g/100 cc, or greater than about 14 g/100 cc, or about It has a butane adsorbing and desorbing capacity of greater than 15 g/100 cc or greater than 20 g/100 cc. Ranges such as about 10-20 g/cc, about 10-12 g/cc, about 10-14 g/cc, about 12-14 g/cc, about 12-15 g/cc and about 15-20 g/cc are also considered

In some embodiments, the stacked sheets are maintained in a spaced relationship that controls one or more of void volume, flow rate, pressure drop, and other properties. This spacing is achieved in some embodiments by pleating at least one of the two or more absorbent sheets. Further, the spacing may be achieved using various folds in the sheets, and may be achieved by corresponding protrusions and/or depressions in the sheets aligned to form gaps between the sheets. Intentionally arranging the sheets so that the protrusions and/or depressions of the sheets do not overlap between the sheets, thereby providing additional spacing between the sheets and enabling fluid flow in those areas. If the sheets are intentionally arranged so that at least some of the protrusions and/or depressions overlap between the sheets, this results in a tighter fit of the stack of sheets and a reduced gap between the sheets, resulting in a corresponding reduction in fluid flow or Even stops are made. A combination of these features can be used to form a laminated absorbent sheet product having directed areas or channels for fluid flow and barriers or edge seals to prevent fluid leakage. Additionally, these features for fluid flow may include holes, cuts or openings through one or more sheets within the laminated absorbent sheet product.

Each absorbent sheet defines opposing side edges that are substantially parallel to the fluid flow. The same side edges of adjacent adsorbent sheets may be separate from each other, joined together, or some combination thereof. In this way, the edge of the laminated absorbent sheet product may be sealed, partially sealed, or unsealed. The sealed or unsealed properties may be selected to achieve a desired result, such as altering fluid flow rates and/or patterns or other properties.

In some embodiments, the layered adsorbent product forms a void volume of about 10% or less. In some embodiments, the void volume is about 8% or less, in some embodiments, the void volume is about 6% or less, and in some embodiments, the void volume is about 4% or less.

In some embodiments, each absorbent sheet has a density of about 0.08 g/cc to about 1.5 g/cc.

In some cases, the absorbent sheet product includes at least two populations of adsorbent particles, each of the at least two populations having a different mean particle diameter. Reference is made to the above description of the bi-circular particle size distribution discussed in relation to the individual adsorbent sheets. An equal distribution ratio between groups of adsorbent particles is considered with respect to products formed from multiple sheets of adsorbent. In some cases, the density of the adsorbent particles achieved by at least two groups is greater than the density achieved by either group alone. In addition, the mechanical properties of the absorbent sheet product can be improved by using a bi-circular particle size distribution, because the distribution makes the polymer sheet much more resistant to shear forces.

In some cases, the absorbent sheet product comprises at least two absorbent sheets having a known total total surface area each defining an upper surface and a lower surface, wherein each absorbent sheet comprises an absorbent material and a binder; The individual sheets of absorbent material are stacked and arranged such that adjacent upper and lower surfaces of the individual sheets are substantially parallel to each other and aligned such that fluid flows between at least the adjacent upper and lower surfaces.

The absorbent sheet product has a BWC stack drainage ratio of about 2.0, where the BWC stack drainage ratio is defined by the equation:

BWC Stacking Drainage Ratio = [ (Measured BWC of the entire adsorbent sheet product) / (BWC of each adsorbent sheet measured externally apart from the above product) ] / number of adsorbent sheets in the adsorbent sheet product.

The BWC stacking multiple ratio is at least about 1.0, at least about 1.1, at least about 1.2, at least about 1.3, at least about 1.4, at least about 1.5, at least about 1.6, at least about 1.7, at least about 1.8, at least about 1.9, at least about 2.0, at least about 2.1, at least about 2.2, at least about 2.3, at least about 2.4, at least about 2.5, at least about 2.6, at least about 2.7, at least about 2.8, at least about 2.9 and at least about 3.0. Additionally, the endpoints can be combined, for example about 1.0-1.5, about 1.1-1.2, about 1.1-1.3, about 1.5-2.0, about 2.0-2.5 and about 2.5-3.0.

The absorbent sheet product of claim 1, wherein the absorbent sheet product has a BWC of about 5%, about 10%, about 15%, about 20%, about 25%, about 30 %, about 35%, about 40%, about 45% and greater than about 50% BWC values. The above values may be combined over the formed range, eg, about 5-25%. The present invention also contemplates when these amounts are at the endpoints on a range, such as at least about 40% greater.

The absorbent sheet in the absorbent sheet product is flat, spirally wound, elliptical, elongated rectangular bar wound, folded, “S” laminated, and concentrically cylindrical. , a shape formed of a concentric ellipse, a shape formed of a concentric rectangular rod, or a combination of the above shapes.

In some embodiments, the absorbent sheet product will comprise a single sheet of absorbent material rolled or rolled to achieve desired properties, including but not limited to density, void space, pressure drop, and the like.

Wrapped/Rolled Sorbent Sheet Products: The absorbent sheet products may alternatively or in combination with laminated embodiments be rolled or rolled. The rolled or rolled absorbent sheet product includes a sheet of absorbent material having a known total surface area defining an upper surface and a lower surface, respectively, wherein the absorbent sheet comprises an absorbent material and a binder, wherein the absorbent sheet is spirally wound. to create adjacent sheet layers that allow fluid to flow around and between adjacent sheet layers.

Similar to the stacked sheet configuration, the rolled absorbent sheet product has improved performance over the absorbent sheet alone and compared to the same weight of activated carbon provided in pelletized or powdered form.

A rolled arrangement leads to an improved BWC for a given sheet area compared to the same area of individual non-rolled sheets. For example, each individual sheet of absorbent material may have a BWC of about 12, and the rolled absorbent sheet media may have a BWC of at least about 1-10%, at least about 5-15%, at least about 2-20% of the sum of the BWCs of the individual sheets. %, at least about 5-10%, at least about 5% or at least about 7% higher BWC.

Further, the performance improvement of the rolled absorbent sheet product of the present invention can be measured as the performance of that product with a given amount of activated carbon relative to the performance of the same amount and grade of activated carbon when provided in pelletized or powdered form in a canister. there is. In some embodiments, the rolled absorbent sheet product contains greater than about 3%, greater than about 5%, greater than about 7%, greater than about 9%, greater than about 9%, relative to the same amount and grade of activated carbon in pelletized or powdered form in a canister. have a BWC that is greater than 10%, greater than about 12%, greater than about 14% and greater than about 16%. Performances in ranges based on these amounts are also contemplated, such as greater than about 5-14%, greater than about 5-10%, greater than about 10-16%, and the like.

The rolled absorbent sheet product has a BWC that is at least 10% greater than the BWC of the same weight of the absorbent in pelletized/powdered form in the absorbent sheet. The roll-type adsorbent sheet product has a butane adsorption and desorption capacity of greater than about 10 g/100 cc. The rolled absorbent sheet product has a weight of from about 7.0 g/100 cc to greater than about 30 g/100 cc, or greater than about 12 g/100 cc, or greater than about 13 g/100 cc, or greater than about 14 g/100 cc, or about It has a butane adsorbing and desorbing capacity of greater than 15 g/100 cc or greater than 20 g/100 cc. Ranges such as about 10-20 g/cc, about 10-12 g/cc, about 10-14 g/cc, about 12-14 g/cc, about 12-15 g/cc and about 15-20 g/cc are also considered

The rolled absorbent sheet products as described herein have a generally cylindrical shape with a length substantially greater than the diameter, although any dimension may be used, including conical or truncated conical variations as well as ellipsoidal or other shapes.

The density of the rolled absorbent sheet product can be calculated based on the following formula:

The roll type absorbent sheet product is about 80-1500 kg/m3, about 500-2000 kg/m3, about 750-1500 kg/m3, about 900-1200 kg/m3, about 900-1050 kg/m3, about 400-500 kg/m3, about 500-600 kg/m3, about 500-550 kg/m3, about 600-650 kg/m3, about 650-700 kg/m3 and about 700-750 kg/m3. can

The roll-type adsorbent sheet product has a butane adsorption and desorption capacity of greater than about 10 g/100 cc. In some embodiments, the rolled absorbent sheet product has a butane adsorbent and desorption capacity of about 7.0 g/100 cc to about 30 g/100 cc. In addition, the roll-type adsorbent sheet product may have the same butane adsorption/desorption capacity as the aforementioned non-roll-type adsorbent sheet product.

Similar to the above discussion with respect to layered adsorbent sheets, the rolled or rolled adsorbent sheet may include a plurality of particle size distributions or groups of particles of pelletized or powdered adsorptive activated carbon. The same ratios as discussed above are contemplated. Similar to the discussion above, this results in better performance because the ratio allows for the inclusion of a large amount of activated carbon in the sheets formed into a rolled absorbent sheet product.

As used herein, a rolled or rolled absorbent sheet product means one or more absorbent materials by winding into a tubular shape (of any cross-sectional shape, such as sphere, oval, square, triangle, rectangle, etc.), spiral winding, concentric layering, or a combination thereof. Refers to any form of stratification of sheets. For example, a single absorbent sheet may be helically wound along its length to form a cylindrically shaped rolled absorbent sheet product. As another example, a plurality of absorbent sheets may be stacked and then wound together to form a similar cylindrical shape. As another alternative, several sheets each formed into a cylinder having a slightly different diameter than adjacent sheets may be arranged so that they form concentric rings in the cross section of a cylinder of similar size. As described elsewhere herein, various combinations of the above and other arrangements may be used to fill a space within a housing or canister of any shape.

As mentioned above with respect to the absorbent sheet, the binder is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF2 or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO) ), UV curable acrylate, UV curable methacrylate, thermoset divinyl ether, polybutylene terephthalate, acetal or polyoxymethylene resin, fluoroelastomer, perfluoroelastomer (FFKM) and/or tetrafluoroethylene/ Propylene rubber (FEPM), aramid polymer, para-aramid polymer, meta-aramid polymer, poly trimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxial oriented polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof.

housing

The present invention also contemplates the use of a housing that partially or fully encloses the absorbent sheet. The housing may be of various shapes, such as tetrahedral, cubic and cubic shapes, cylindrical, spherical, single sheet hyperboloidal, conical, elliptical, rectangular, hyperbolic, parabolic, elongated rod, parabolic and combinations of these shapes. may consist of The combination may be chosen to have different sections, each having a different shape or a part of a different shape. The housing may include sections separated and connected by additional components, for example at least one hose or tube designed to deliver fuel vapor as required, or a thin section of the housing comprising a sheet of absorbent material. The housing may also be configured without a shape, for example as a flexible bag or pouch containing a sheet of absorbent material.

One major advantage of the present invention is that the use of the absorbent sheet is both flexible and self-supporting, and the sheet can be laminated, rolled, rolled, folded, or stacked into various configurations within the housing, so that the vehicle's It is possible to fit different mechanical requirements within a tight confined area. In such an embodiment, the housing will match or be designed to fit a space in which the device can be stored. For example, housings may include wheel wells, drive shafts, batteries for hybrid powertrains, spare tires, tire changing tools, tire patching tools, vehicle trunks or other storage spaces, vehicle bumpers and body metal plates, and exhaust systems. , other emission control equipment, such as urea or other injection tanks, fuel lines, vehicle frames, suspension components, engine compartments, under passenger compartment seats, inside passenger compartment seats, and others that are too narrow or too difficult to effectively use as passenger or cargo space. They can be sized and shaped to fit within or around the spaces.

To further reduce weight and size and to utilize a self-supporting absorbent sheet, the housing may be in the form of a thin walled bag or pouch. This is possible because the absorbent sheet has some mechanical structure to support itself and therefore does not require a rigid outer container as in conventional canisters. The film material forming the bag may have a thickness of about 10 μm to about 250 μm. In another embodiment, the thickness of the bag film can be from about 20 μm to about 175 μm, and the thickness of the bag film can be from about 50 μm to about 125 μm.

The bag or pouch may be made of any material used in fuel systems, but is made of materials specifically designed to withstand the chemical effects of the fuel vapors in which it is contained. Bag materials include polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable acrylate, UV curable methacrylates, thermoset divinyl ethers, polybutylene terephthalate, acetal or polyoxymethylene resins, fluoroelastomers such as perfluoroelastomers (FFKM) and tetrafluoroethylene/propylene rubber (FEPM), aramid polymers such as para- Aramid and meta-aramid polymers, polytrimethylene terephthalate, ethylene acrylic elastomers, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP), polyethylene terephthalate (PET ), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof. The bag is usually thermoplastic for flexibility, but may be in combination with an amount of a thermosetting agent, or may be in the form of a cured rubber or elastomer.

The housing, bag or pouch may be designed to act as a vapor barrier to adsorbed fuel vapor contained therein. These barrier properties may be inherent to the polymer itself or may be achieved through the use of at least one barrier additive and/or at least one barrier layer. Examples of barrier additives that can be formulated as layers or particulate fillers include epoxies, polyamides, polyamide imides, fluoropolymers, polymers such as fluororubbers, and combinations thereof. The barrier layer may be made of metals such as aluminum, steel, titanium and alloys thereof. The metal barrier layers may be formed by conventional mechanical methods such as coextrusion or bonding with other layers of the housing, or they may be chemically deposited, for example by chemical vapor deposition or electroplating. The metal barrier layer can be made from a foil having a thickness of less than about 25 μm, less than about 20 μm, less than about 15 μm, less than about 10 μm or less than about 5 μm.

The housing and its materials may be selected to be compatible with a “ship in a bottle” fuel system. In such systems, many or all of the fuel system components, including fuel pumps, ORVRs, fuel filters, valves and other components, are mounted within the vehicle fuel tank. Such a system is advantageous because it reduces the extent of assembly time and space required for the fuel system. In such a system, the housing must contain a material capable of being immersed in the selected fuel, usually gasoline, for a long time in the vehicle fuel tank, while also being capable of withstanding the effects of fuel vapor adsorbed therein.

Also, the housing may be a thin metal housing. The thin metal housing may be made of a flexible or rigid metal such as steel, aluminum, titanium and alloys thereof. The metal housing may be made of a foil having a thickness of about 5-100 μm or about 10-250 μm. In some embodiments, the foil may be about 1 mm thick. Whether the housing is flexible or rigid depends on the choice of material, its thickness and any treatment applied to the metal, such as heat treatment or hot or cold work.

In some embodiments, the housing for the absorbent sheet may be omitted entirely with the absorbent sheet contained within the fuel tank itself. In this configuration, the adsorbent sheet can be attached to a part inside the fuel tank that is not in regular contact with liquid fuel and freely absorbs fuel vapor. The portion is typically the top or side of the fuel tank, or a combination thereof. The fuel tank may include an adsorbent sheet including a recess in the top or side designed to adsorb fuel vapor. This embodiment in which the absorbent sheet is attached to the inside of the fuel tank not only provides maximum space savings and weight savings by omitting the canister structure, but also manufactures because the sheets are already installed in the fuel tank during vehicle assembly. and installation can be simplified.

It is also possible to eliminate the housing by selectively curing the outer sheet after fabrication of the rolled or folded absorbent sheet so that they form a durable, cured shell that acts as a support for the rolled or folded absorbent sheet. This selective curing can be accomplished using heat, or using a chemical bath, or through actinic radiation such as ultraviolet light, or by electron beam curing.

In embodiments where the absorbent sheet omit the housing and is contained within the vehicle fuel tank itself, the absorbent sheet may be attached to the fuel tank in a variety of ways. The absorbent sheet may be secured using mechanical fasteners such as screws, rivets or clamps, or the absorbent sheet may be secured using an adhesive backing placed between the fuel tank wall and the absorbent sheet. The adhesive backing may be a single layer of adhesive or a double sided adhesive tape or sheet. Adhesives used for the adhesive backing may include pressure sensitive adhesives, UV curable adhesives, thermosetting adhesives, hot melt adhesives and reactive multicomponent adhesives. Adhesive compositions include acrylics and (meth)acrylics, acrylates and (meth)acrylates, epoxies and urethanes in one-part and two-part formulations.

The absorbent sheet may be applied in a variety of ways during manufacture. In some embodiments, the fuel tank may be formed and the absorbent sheet applied in a separate step of applying the absorbent sheet after the adhesive is applied. In another embodiment, the absorbent sheet is placed inside the mold, with or without an adhesive backing, and the fuel tank is injection or blow molded around the absorbent sheet. In another embodiment, the absorbent sheet may be co-extruded with the panels of material that make up the sides of the fuel tank, the edges of which are glued or welded together to seal the fuel tank with the absorbent sheet therein. .

When the absorbent sheet is contained within a vehicle fuel tank without a housing, the fuel tank may include additional valves and ports to accommodate adsorption and desorption of fuel vapor within the fuel tank. For example, while the engine is running, air may flow into the fuel tank and desorb fuel vapor contained in the adsorbent sheet as well as vapor present in the tank. This desorbed fuel vapor is then sent to the engine for combustion during the optimal cycle required by the ECU.

When the absorbent sheets are provided without a housing and are contained within a tank, such as a vehicle fuel tank, they may be positioned so as not to be regularly immersed in volatile liquids normally contained within the tank. This prevents the adsorbent sheet from becoming saturated prematurely and also allows sufficient surface area to be exposed to the vapor in the fuel tank for effective vapor adsorption. The feature also contemplates that the adsorbent sheet may be placed near a portion of the tank that is not filled, such as a void or void in the tank, or a partition that prevents sloshing of liquid on the adsorbent sheet. The adsorbent sheet may be placed in a dedicated part of the tank, such as a small chamber, or where liquid cannot enter.

Devices of various embodiments may include a housing and the absorbent sheets described above. The housing may be of any shape and may be configured to purify a gas or liquid. For example, in some embodiments, the housing can be of any shape, such as, for example, cubic, cuboidal, or cylindrical. The adsorbent sheet may be sized to fit within the housing and substantially fill a space within the housing through which the gas or liquid passes. In some embodiments, two or more absorbent sheets may be stacked to substantially fill a housing, and in other embodiments, the absorbent sheets may be rolled to form a spirally wound sheet or pressed to form a stacked sheet. . In some embodiments, laminated or pressed sheets may have sides of adjacent sheets substantially continuous. In other embodiments, laminated or pressed sheets may be positioned such that adjacent sheets are spaced apart. For example, in certain embodiments, the sheets may be pleated with absorbent sheets forming series or parallel ridges and grooves, and in some embodiments, the pleated absorbent sheets may be separated by planar absorbent sheets. there is. The pleated adsorbent sheet may be disposed in a housing in a stacked or rolled/spiral wound form.

In various embodiments, the porosity can be about 30% to about 32% less than the void volume in current devices, and in some embodiments, the porosity can be less than 10%. For example, the device may have a porosity of about 45% to about 2%, about 35% to about 5%, about 25% to about 7%, or any individual porosity or porosity range included in these exemplary ranges. can Devices of various embodiments may have less flow restrictions, such as pressure drop, than granulated or pelletized adsorbents. Thus, more adsorbent can be incorporated into the device without reducing the flow rate of the device.

The devices of these embodiments may have a butane adsorption and desorption capacity ("BWC") of greater than about 5.0 g/100 cc, and in some embodiments, the devices may have from about 4.0 g/100 cc to about 20 g/100 cc, BWC of 5.0 g/100 cc to about 18 g/100 cc, about 7.0 g/100 cc to about 16 g/100 cc, or about 8.0 g/100 cc to about 15 g/100 cc, or in these exemplary ranges It may have any individual BWC or BWC range included. The device can exhibit approximately the same pressure drop as a conventional dense pack bed of powders, pellets or granules of activated carbon or other activated compounds. These features enable the absorbent sheet products of the present invention, stacked, rolled, wound or otherwise constructed, to still have the same vapor and gas handling and delivery capabilities as conventional devices, even with increased adsorption performance. It is advantageous because it

When the stacked or rolled absorbent product is coupled with a housing, it is useful as a vapor loss canister or other device. As noted above, the shapes and properties achieved through laminated or rolled products allow for unique placement and improved performance.

In accordance with some embodiments, a vapor loss canister includes a housing having at least one sidewall defining an interior space, a sorbent sheet product, wherein the sorbent sheet media fits within the housing to substantially fill the entire interior space within the housing. The interior space is substantially free of additional interior material other than adsorbent sheet media. In other words, conventional vapor loss canisters require springs, filters, support substrates, etc. to retain and retain the coarse carbon powder or pellets. Since the present adsorbent sheet is substantially self-supporting, no such additional support structure is required. This allows for more material or smaller canisters to be used without sacrificing performance.

In some embodiments, the absorbent sheet product comprises a layered absorbent sheet media including those described above. In this case, the housing or canister can take any shape as discussed above, but in some embodiments is relatively planar and flexible to house a layered absorbent sheet having a height substantially less than its length or width. . In this case, the housing may be a flexible bag or pouch, as described above.

In some cases, the canister is configured to be disposed on top of or even inside the fuel tank.

In some embodiments, the absorbent sheet product comprises a rolled absorbent sheet product as described above. In some cases, at least a portion of the housing sidewall forms a filter that does not occupy substantially any interior canister space.

In some embodiments, the fuel tank may be provided with the requisite vapor adsorption function. Such a tank includes a tank structure and at least one absorbent sheet product, either laminated or rolled, and at least one securing device for securing the absorbent product to a surface of the tank that is not regularly immersed in the volatile liquid contained within the tank. . The anchoring device may be an adhesive layer formed between one surface of the absorbent article and the wall of the tank.

These adhesives include pressure sensitive adhesives, UV curable adhesives, thermosetting adhesives, hot melt adhesives, reactive multi-component adhesives, acrylic and (meth)acrylic adhesives, acrylate and (meth)acrylate adhesives, epoxy adhesives in one- or two-component formulations. , urethane adhesives, and copolymers and combinations thereof.

The tank further comprises one or more of at least one fuel pump, fuel supply line, fuel return line, atmospheric exhaust line, ports, valves, sensors, air intakes, open-pore foam, baffles, bladders, and combinations of the foregoing. can include

In some embodiments, the tank is a fuel tank having a “ship in a bottle” configuration.

Some embodiments provide an onboard fuel vapor recovery device comprising a sorbent sheet product described herein. The onboard refueling vapor recovery device may include the vapor adsorption canister described herein. The on-board fueling vapor recovery device may include a tank having the essential vapor adsorption function of claim 22.

additional parts

The present invention may include a sensor, such as a fuel composition sensor. The fuel composition sensor can be used to detect a mixture of gasoline, ethanol, and adsorbent contained in the housing, and this information is transmitted to the ECU so that steam emitted to the engine can be more accurately used during engine combustion. Other sensors include temperature sensors, vapor pressure sensors, oxygen sensors, and the like. The sensors may operate according to the principles of electrochemical interaction, electronics such as thermocouples, electromechanical interaction, refractive index, infrared spectroscopy, etc., depending on the type of information required by the ECU. The sensors may be included singly or in combination within the housing, and if the housing is not specified, they may be included within the area including the absorbent sheet. The sensors may be included in a hole or notch cut out of the sheet, or may be included in a space between sheets wrapped around or folded around the sensor.

The invention may include inlets, outlets, hoses and associated valves for controlling the flow of fuel vapor to and from the sorbent of the present invention. The openings may be stationary or may have valves that open and close as required by the ECU to control the flow of vapor into and out of the adsorbent sheet of the present invention. During refueling, for example, the outlet valve is kept closed to prevent vented fuel vapor from escaping to the atmosphere. However, when the engine is running and the ECU requests it, at least one outlet valve can be opened to release the adsorbed vapor into the engine for combustion. Vents and valves to atmosphere may also be included if too much fuel vapor is present for the absorbent sheet of the present invention to safely adsorb. Inlets and valves may also be included for other gases, such as air or inert exhaust gas, used to desorb the fuel vapor as it is sent to the engine for combustion.

The present invention also contemplates the inclusion and integration of other components that make up ORVR systems and devices. These other components include active compressors and condensers, fuel tank heaters, fuel tank heat exchange coils for cooling enclosed fuel, fuel filler necks, fuel filler ports including uncapped fuel filler ports, exhaust vents for fuel vapors, and fuel delivery. fuel lines, fuel return lines, exhaust vents and vehicle rollover valves, fuel pumps, and air intake or purge valves.

In addition, the present invention further contemplates devices and structures that may be combined with adsorbent sheets to improve or control the adsorption and desorption of fluids and gases. For example, when assembling sheets of sorbent material, a fan or pump may be included to force fluid or vapor onto the sheets, thereby making the sorbent material different than would otherwise be possible with the same amount of fluid spreading across the sheet. The sheets may be more densely packed or wound, or may allow for larger devices. Alternatively, the device may include a resistive element heater or Peltier effect heater or cooler designed to heat and/or cool the fluid and force the fluid onto the absorbent sheet of the claimed invention. . For example, heated and expanded fluid may be discharged upwards, drawing more fluid from the bottom of a vertically oriented rolled or wound article to exploit the effects of gravity.

Other uses

In addition to automotive applications, the inventors contemplate that the absorbent sheet of the claimed invention may also be used where tanks or other confined spaces are designed to contain volatile liquids, particularly fuels, volatile hydrocarbons such as solvents, and other volatile compounds. Examples include, but are not limited to, fuel tanks in aircraft, fuel tanks in ships and other marine vehicles, fuel tanks in trucks, chemical tanks in railroad cars, barges, ships, trucks, vehicles and other bulk carriers and stationary chemical including the tank In addition, the adsorbent sheet of the claimed invention can be adhered to or adhered to the walls of confined spaces where the presence of volatile compounds can be detrimental, for example in chemical facilities where operators and maintenance personnel must periodically access the space. there is. Such adsorbent sheets, when used in the converged space, can increase the safety of operators and maintenance personnel as well as reduce the need for cumbersome and complicated protective equipment.

In some embodiments, the device may not filter out fine particles, which would be useful outside a fuel vapor recovery area. Devices containing granular or pelletized sorbents filter particles greater than about 1% of their diameter and remove these particles from the gas or liquid being treated with the device. Since devices containing laminated or roll/spirally wound sheets of absorbent material allow these particles to pass through without filtering, the devices of various embodiments may be useful for filtering biological fluids such as blood, in which case red blood cells and white blood cells and platelets etc. must pass through a filter without being physically filtered from the blood. Other contaminants can be adsorbed on the sheet of sorbent material and removed from the blood filtrate.

Example

Although the present invention has been described in great detail with respect to certain preferred embodiments, other embodiments versions are possible. Accordingly, the concept and scope of the appended claims should not be limited to the detailed description and preferred embodiment versions contained within this specification. Various aspects of the present invention will be illustrated with reference to the following non-limiting examples.

As discussed above, BWC is a measure of the performance of activated carbon. BWC is measured by measuring the ability of activated carbon to adsorb and desorb butane from dry air under specified conditions for a sample, and measures the difference between the butane adsorbed at saturation and the butane retained per unit volume of carbon after a defined purge. . BWC can be tested in a number of ways, including procedures defined by ASTM International and known to those skilled in the art. Specifically, the test may follow ASTM D5228 [revisions D5228-16, D5228-92 (2015), D5228-92 (2005) and D5228-92 (2000)].

In Examples 1-4, carbon sheets were helically wound to obtain a porosity of 10%, which provides about a 30% performance improvement over activated carbon ("PAC") alone. Similar to Comparative Example 1, the porosity of the granulated or powdered layer of comparative activated carbon was about 40% by volume. Hereinafter, Examples and Comparative Examples will be described.

Example 1

Activated carbon films were made from CPL (CT#14299-8), a wood-based activated carbon activated using phosphoric acid. Additionally, the film was made with CPW (CT#14299-10), a wood-based activated carbon activated using phosphoric acid. The activated carbon was ground in a mechanical mortar and pestle and mixed with 9% PTFE powder. The resulting composition exhibited a viscosity similar to bread dough. The composition was rolled to a thickness of 0.448 mm (CT#14299-8 1), 0.411 mm (CT#14299-8 2), 0.459 mm (CT#14299-10 1) and 0.439 mm (CT#14299-10 2) A sheet having was formed.

Example 2

Activated carbon sheets were prepared as described in Example 1 using BVC-11 8x25 activated carbon, a nutshell based activated carbon activated with phosphoric acid. This formed sample CT#14266-1. A sample was also prepared using BVC-11 8x35, an activated carbon based on nutshells and activated with phosphoric acid. This formed sample CT#14266-2. The thickness of the formed sheets was 0.330 mm (CT#14266-1 1), 0.334 mm (CT#14266-1 2), 0.327 mm (CT#14266-1 3), 0.317 mm (CT#14266-2 1), 0.307 mm (CT#14266-2 2) and 0.328 mm (CT#14266-2 3).

Butane adsorption/desorption test - Examples 1 and 2

Using the butane adsorption and desorption test, the activated carbon sheets prepared in Examples 1 and 2 were tested for butane adsorption. In this test, sheets were rolled and placed in a tube. Butane was added to the tube and butane adsorption was measured. The tactic experiments used to predict BWC performance were performed on small stacks of 5 piece sheets. The results are shown in Tables 1 and 2:

Example 3

Activated carbon sheets were prepared as in Examples 1 and 2 except that granular activated carbon #3445-32-4 was used. The activated carbon sheet was also not tightly rolled as in Examples 1 and 2 above. The resulting sheets were tested for butane adsorption using a butane adsorption and desorption capability test. In the above two experiments, two individual laminates of 20 sheets of 0.45 mm thickness were cut into rectangles of 2.2 cm X 7.5 cm ± 10%, and the side edges were sealed with 0.05 mm thickness and 2 mm width double-sided tape. In this configuration, the tape thickness formed the average sheet spacing. The total height of each stack of 20 sheets with tape space was 1 cm. The sheet stack was placed in a large cylindrical glass tube with a diameter of 2.54 cm for butane adsorption/desorption tests. The excess volume between the rectangular sheet stack and the wall of the cylindrical glass tube is filled with closed cell expanded foam to absorb the excess volume and seal to prevent bypass gas flow past the inserted test sample. did Butane or air was forced into a 0.05 mm gap between 20 sheets. Flow rates and volumes for the sheet stack were selected to comply with the ASTM working capacity procedure. The ASTM procedure was followed except for the use of a stack of sheets rather than a granular layer, the use of closed-pore expandable foam for sealing, and the larger cylindrical glass tube arrangement needed to accommodate the rectangular stack of sheets.

During the above modified ASTM procedure, butane or air was forced into the 0.05 mm gap between the 20 sheets, and the flow rates and volumes for the sheet stack were maintained at ASTM specifications for working capacity. The results of Example 3 are shown in Table 3 below.

Comparative Example 1

A comparative example was also prepared using the same granular activated carbon as in Example 4, #3445-32-4, except that the granular activated carbon was not formed as part of a sheet or roll. The granular activated carbon was tested according to ASTM procedures. The results of the test are shown in Table 3 below.

Conclusions and Summary for Examples 1-3 and Comparative Example 1

Relevant data are summarized in Table 4 below:

Claims (45)

As a sorbent material sheet product,
comprising at least two adsorbent sheets, each adsorbent sheet having a defined upper and lower surface as an overall total surface area, each adsorbent sheet comprising an adsorbent and a binder, and adjacent upper and lower surfaces of the individual sheets being parallel and wherein each absorbent sheet product is stacked and arranged such that fluid flows between at least the adjacent upper and lower surfaces, wherein the absorbent sheet product has a void volume of less than 10%. The absorbent sheet product of claim 1 , wherein the absorbent sheet product has a BWC stacking multiplier ratio of 1.1 to 1.3, wherein the BWC stacking multiplier ratio is defined by the formula:
BWC Stacking Drainage Ratio = [ (Measured BWC of the entire adsorbent sheet product) / (BWC of each adsorbent sheet measured externally apart from the above product) ] / number of adsorbent sheets in the adsorbent sheet product. 2. The absorbent sheet product of claim 1, wherein the individual absorbent sheets, when measured individually, have a BWC value that is 5-15% greater than the BWC of the same weight of the absorbent in pelletized or powdered form. The method of claim 1, wherein the at least one absorbent sheet is flat, spirally wound, elliptical, elongated rectangular bar wound, folded, “S” laminated, An absorbent sheet product comprising a shape formed of concentric cylinders, a shape formed of concentric ellipses, a shape formed of concentric rectangular rods, or a combination of the above shapes. The absorbent sheet product of claim 1 , wherein the at least one absorbent sheet has protrusions and/or depressions. 6. The absorbent sheet product of claim 5, wherein the protrusions and/or depressions are present and nested on adjacent sheets. 6. The absorbent sheet product of claim 5, wherein the protrusions and/or depressions are on adjacent sheets and are not overlapping. delete The absorbent sheet product of claim 1 , wherein each individual absorbent sheet has a density of from 0.08 g/cc to 1.5 g/cc. The absorbent sheet product of claim 1 , wherein the absorbent sheet product has a BWC of greater than 10 g/100 cc. The absorbent sheet product of claim 1 , wherein the absorbent sheet product has a BWC of 7.0 g/100 cc to 30 g/100 cc. The method of claim 1, wherein the adsorbent sheet includes adsorbent particles having at least two groups of different average particle diameters, and the ratio of the average particle diameters of the two groups is from 1:2 to 1:10. absorbent sheet products. 2. The absorbent sheet product of claim 1, wherein the amount of binder and the amount of absorbent sheet product are in a gradient such that the amount of binder is highest on the outside of the absorbent sheet product and lowest on the inside of the absorbent sheet product. The absorbent sheet product of claim 1 , wherein the at least one absorbent sheet comprises holes, cutouts or openings. The method of claim 1, wherein the binder is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable Acrylates, UV curable methacrylates, thermoset divinyl ethers, polybutylene terephthalates, acetal or polyoxymethylene resins, fluoroelastomers, perfluoroelastomers (FFKM) and/or tetrafluoroethylene/propylene rubber (FEPM) ), aramid polymer, para-aramid polymer, meta-aramid polymer, polytrimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene ( BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof. As a rolled absorbent sheet product,
An adsorbent sheet having a defined upper surface and a lower surface as a total surface area, comprising an adsorbent and a binder,
wherein the absorbent sheet is helically wound to form adjacent sheet layers allowing fluid to flow around and between the adjacent sheet layers;
The rolled absorbent sheet product, wherein the absorbent sheet product has a void volume of 10% or less. 17. The rolled absorbent sheet product of claim 16, wherein the rolled absorbent sheet has a BWC that is at least 10% greater than the BWC of the same non-rolled absorbent sheet. 17. The rolled absorbent sheet product of claim 16, wherein the rolled absorbent sheet product has a BWC of at least 10% greater than the BWC of an equivalent amount of the absorbent in pelletized or powdered form within the absorbent sheet. 17. The rolled absorbent sheet product of claim 16, wherein the rolled absorbent sheet product has a generally cylindrical shape with a length greater than a diameter. The rolled absorbent sheet product according to claim 16, wherein the rolled absorbent sheet product is wound at an average roll density of 500-700 kg/m 3 . 17. The rolled absorbent sheet product of claim 16, wherein the rolled absorbent sheet product has a butane working capacity greater than 10 g/100 cc. The rolled absorbent sheet product according to claim 16, wherein the rolled absorbent sheet product has a butane adsorption/desorption capability of 7.0 g/100 cc to 30 g/100 cc. 17. The rolled absorbent sheet product of claim 16, wherein the rolled absorbent sheet comprises at least two groups of absorbent particles, each group of the at least two groups having a different average particle diameter. The method of claim 16, wherein the roll-shaped adsorbent sheet includes adsorbent particles having at least two groups of different average particle diameters, and the ratio of the average particle diameters of the two groups is 1:2 to 1:10. , roll type adsorbent sheet products. 17. The method of claim 16, wherein the binder is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable Acrylates, UV curable methacrylates, thermoset divinyl ethers, polybutylene terephthalates, acetal or polyoxymethylene resins, fluoroelastomers, perfluoroelastomers (FFKM) and/or tetrafluoroethylene/propylene rubber (FEPM) ), aramid polymer, para-aramid polymer, meta-aramid polymer, polytrimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene ( BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof. The absorbent sheet product of claim 1, and
A housing at least partially enclosing the absorbent sheet product of claim 1
A canister for vapor adsorption comprising a. 27. The canister of claim 26, wherein the housing is flexible. 27. The method of claim 26, wherein the housing is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable Acrylates, UV curable methacrylates, thermoset divinyl ethers, polybutylene terephthalates, acetal or polyoxymethylene resins, fluoroelastomers perfluoroelastomers (FFKM) and/or tetrafluoroethylene/propylene rubber (FEPM) , aramid polymer, para-aramid, meta-aramid polymer, polytrimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP) , polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof. 27. The canister of claim 26, wherein the shape of the housing matches the shape of the absorbent sheet product of claim 1 contained therein. 27. The canister of claim 26, further comprising at least one structure selected from tubes, inlets, outlets, sensors, valves and fluid channels. The rolled absorbent sheet product of claim 16, and
A housing at least partially enclosing the rolled absorbent sheet product of claim 16
A canister for vapor adsorption comprising a. 32. The canister of claim 31, wherein the housing is flexible. 32. The method of claim 31, wherein the housing is polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF ₂ or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable Acrylates, UV curable methacrylates, thermoset divinyl ethers, polybutylene terephthalates, acetal or polyoxymethylene resins, fluoroelastomers perfluoroelastomers (FFKM) and/or tetrafluoroethylene/propylene rubber (FEPM) , aramid polymer, para-aramid, meta-aramid polymer, polytrimethylene terephthalate, ethylene acrylic elastomer, polyimide, polyamide-imide, polyurethane, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP) , polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers and combinations thereof. 32. The canister according to claim 31, wherein the shape of the housing matches the shape of the rolled absorbent sheet product of claim 16 contained therein. 32. The canister of claim 31 further comprising at least one structure selected from tubes, inlets, outlets, sensors, valves and fluid channels. As a tank having an essential vapor adsorption function,
tank structure;
at least one adsorbent sheet having a defined upper and lower surface of each sheet as total total surface area, each adsorbent sheet having at least two groups of different average particle diameters, wherein the ratio of the average particle diameters of the two groups is An adsorbent sheet comprising adsorbent particles in a ratio of 1:2 to 1:10, and a binder; and
and at least one anchoring device for anchoring the adsorbent sheet to a surface of the tank that is not regularly immersed in the volatile liquid contained within the tank. 37. The tank of claim 36, wherein the securing device is an adhesive layer formed between one side of the absorbent sheet and the wall of the tank. 38. The method of claim 37, wherein the adhesive is a pressure sensitive adhesive, UV curable adhesive, thermosetting adhesive, hot melt adhesive, reactive multi-part adhesive, acrylic and (meth)acrylic adhesive, acrylate and ( meth)acrylate adhesives, epoxy adhesives in one- or two-component formulations, urethane adhesives, and copolymers and combinations thereof. 37. The method of claim 36, wherein the tank comprises a fuel pump, a fuel supply line, a fuel return line, an atmospheric exhaust line, a port, a valve, a sensor, an air intake, an open cell foam, a baffle, a bladder ( bladder) and at least one of combinations of the foregoing. 37. The tank of claim 36, wherein the tank is a fuel tank in a "ship in a bottle" configuration. An onboard refueling vapor recovery apparatus comprising the absorbent sheet product of claim 1. An onboard fueling vapor recovery device comprising the roll-type adsorbent sheet product of claim 16. An onboard fueling vapor recovery device comprising the vapor adsorption canister of claim 26. An onboard fueling vapor recovery device comprising the vapor adsorption canister of claim 31. An onboard fueling vapor recovery device comprising a tank having the essential vapor adsorption function of claim 36.